Glycols and methanol are commonly used to inhibit the formation of natural gas clathrate hydrates in pipelines and flow lines in fluid handling systems which convey fluids containing natural gas from oil and gas production sites to oil and gas processing facilities. Glycol is also known as monoethylene glycol, MEG, ethylene glycol, ethylene alcohol, ethane-1,2-diol, and 1,2-ethanediol. Such hydrates are formed from hydrocarbon gases such as methane in the presence of free water at high pressures and low temperatures. Hydrates can accumulate to block pipelines and flow lines, thus impeding production.
In many circumstances, glycol is preferred as a hydrate inhibitor over methanol as glycol has lower flammability risk and is easy to recover and reuse. However, the recovery of glycol introduces potential for exposure to air and specifically to oxygen. Oxygen contamination in glycol systems increases corrosion risk in pipelines, flow lines and other exposed equipment. These risks increase as glycols oxidize and decompose to form organic acids, particularly at higher temperatures. The presence of oxygen can interfere with corrosion inhibitors, exacerbate corrosion rates of iron and many other metals by methods including carbon dioxide and hydrogen sulfide corrosion mechanisms, and encourage aerobic bacteria to grow which can further promote pitting of equipment.
One known method for managing these risks is to use nitrogen or a blanket of dry hydrocarbon gas to exclude oxygen from glycol storage tanks, sumps and other sources of oxygen ingress. The use of nitrogen as a blanket gas has not been effective to eliminate oxygen, as low-grade nitrogen can have an oxygen content of between 3 and 5 vol %. Even high purity nitrogen produced by the cryogenic distillation of air can have an oxygen content of up to 10 ppm. The use of a hydrocarbon blanket gas can be more effective at eliminating oxygen, but introduces flammability and explosion risks.
Another known method for managing these risks is to use chemicals such as oxygen scavengers and oxidation inhibitors. However, such methods have been developed based on pure water systems which raise concerns regarding efficacy in the presence of glycol due to reaction kinetics.
It would be desirable to maintain an oxygen content in the process stream of less than 20 ppb to avoid problems with corrosion, pitting, cracking and the like. Such a low level has been difficult to achieve, monitor and enforce.